Surface Forces, Supramolecular Polymers, and Inversion Symmetry

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Abstract
The effects of supramolecular equilibrium polymers on surface forces are studied by both a phenomenological Landau type analysis and a molecular model based on a Bethe−Guggenheim approximation. We point out that surface forces brought about by equilibrium polymers may be completely different from what can be found with “ordinary” polymers. The new feature is the role of inversion (a)symmetry or “directionality” of the associating unit molecules (“monomers”). Symmetric B−B monomers (where B denotes a self-complementary binding group) give rise to nondirectional chains and lead to attractive forces between similar surfaces. Asymmetric A−D monomers (where A and D denote complementary acceptor and donor groups, respectively) produce directional chains and can cause strong repulsion. The range of the attractive force has a maximum at intermediate concentration, while the range of the repulsive force increases over the whole concentration range.